On the effect of Ga and In substitutions in the Ca₁₁Bi₁₀ and Yb₁₁Bi₁₀ bis­muthides crystallizing in the tetra­gonal Ho₁₁Ge₁₀ structure type

The Ga- and In-substituted bis­muthides Ca₁₁Ga_xBi_10–x, Ca₁₁In_xBi_10–x, Yb₁₁Ga_xBi_10–x, and Yb₁₁In_xBi_10–x (x < 2) can be readily synthesized employing molten Ga or In metals as fluxes. They crystallize in the tetra­gonal space group I4/mmm and adopt the Ho₁₁Ge₁₀ structure type (Pearson code tI84; Wyckoff sequence n2 m j h2 e2 d). The structural response to the substitution of Bi with smaller and electron-poorer In or Ga has been studied by single-crystal X-ray diffraction methods for the case of Ca₁₁In_xBi_10–x [x = 1.73 (2); octabismuth undecacalcium diindium]. The refinements show that the In atoms substitute Bi only at the 8h site. The refined inter­atomic distances show an unconventional – for this structure type – bond-length distribution within the anionic sublattice. The latter can be viewed as consisting of isolated Bi³⁻ anions and [In₄Bi₈²⁰⁻] clusters for the idealized Ca₁₁In₂Bi₈ model. Formal electron counting and first-principle calculations show that the peculiar bonding in this compound drives the system toward an electron-precise state, thereby stabilizing the observed bond-length pattern.

Computing details

Data collection: SMART (Bruker, 2014); cell refinement: SAINT (Bruker, 2014); data reduction: SAINT (Bruker, 2014); program(s) used to solve structure: SHELXTL (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: DIAMOND (Brandenburg, 2014); software used to prepare material for publication: publCIF (Westrip, 2010).

Octabismuth undecacalcium diindium

Crystal data

Bi8.27Ca11In1.73	Dx = 5.913 Mg m^−3
Mr = 2368.25	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I4/mmm	Cell parameters from 505 reflections
a = 12.3534 (19) Å	θ = 4.7–21.1°
c = 17.433 (3) Å	µ = 58.09 mm^−1
V = 2660.3 (9) Å^3	T = 200 K
Z = 4	Block, black
F(000) = 3965	0.14 × 0.07 × 0.03 mm

Data collection

Bruker APEX diffractometer	746 reflections with I > 2σ(I)
Radiation source: sealed tube	Rint = 0.131
phi and ω scans	θmax = 28.1°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2014)	h = −16→16
Tmin = 0.294, Tmax = 0.492	k = −16→16
10649 measured reflections	l = −22→22
975 independent reflections

Refinement

Refinement on F^2	40 parameters
Least-squares matrix: full	0 restraints
R[F^2 > 2σ(F^2)] = 0.038	w = 1/[σ^2(Fo^2) + 13.3889P] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.078	(Δ/σ)max < 0.001
S = 1.07	Δρmax = 2.60 e Å^−3
975 reflections	Δρmin = −2.19 e Å^−3

Special details

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq	Occ. (<1)
Ca1	0.0000	0.2515 (3)	0.3101 (2)	0.0195 (8)
Ca2	0.0000	0.3401 (3)	0.1022 (2)	0.0145 (7)
Ca3	0.3333 (4)	0.3333 (4)	0.0000	0.0342 (15)
Ca4	0.0000	0.0000	0.1652 (4)	0.0158 (15)
Bi1	0.20210 (4)	0.20210 (4)	0.16369 (4)	0.01719 (19)
Bi2	0.15411 (7)	0.5000	0.0000	0.0132 (2)
In3	0.12218 (10)	0.12218 (10)	0.0000	0.0208 (6)	0.859 (9)
Bi3	0.12218 (10)	0.12218 (10)	0.0000	0.0208 (6)	0.141 (9)
Bi4	0.0000	0.0000	0.36826 (8)	0.0141 (3)
Bi5	0.0000	0.5000	0.2500	0.0110 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Ca1	0.027 (2)	0.0147 (18)	0.0164 (19)	0.000	0.000	0.0009 (16)
Ca2	0.0127 (17)	0.0164 (17)	0.0142 (18)	0.000	0.000	−0.0016 (15)
Ca3	0.040 (2)	0.040 (2)	0.022 (3)	0.028 (3)	0.000	0.000
Ca4	0.015 (2)	0.015 (2)	0.017 (4)	0.000	0.000	0.000
Bi1	0.0147 (2)	0.0147 (2)	0.0223 (4)	0.0034 (3)	−0.0003 (2)	−0.0003 (2)
Bi2	0.0119 (4)	0.0139 (5)	0.0139 (5)	0.000	0.000	0.000
In3	0.0236 (7)	0.0236 (7)	0.0150 (10)	0.0017 (7)	0.000	0.000
Bi3	0.0236 (7)	0.0236 (7)	0.0150 (10)	0.0017 (7)	0.000	0.000
Bi4	0.0129 (4)	0.0129 (4)	0.0166 (7)	0.000	0.000	0.000
Bi5	0.0114 (4)	0.0114 (4)	0.0104 (7)	0.000	0.000	0.000

Geometric parameters (Å, º)

Ca1—Bi5	3.244 (4)	Ca4—In3^xv	3.585 (6)
Ca1—Bi4	3.268 (4)	Ca4—Bi3^ii	3.585 (6)
Ca1—Bi2^i	3.509 (4)	Ca4—Bi3^xvi	3.585 (6)
Ca1—Bi1	3.622 (3)	Ca4—In3^ii	3.585 (6)
Ca1—Bi1^ii	3.623 (3)	Ca4—In3^xvi	3.585 (6)
Ca1—Bi1^iii	3.7523 (11)	Bi1—In3	3.1768 (11)
Ca1—Bi1^iv	3.7523 (11)	Bi1—Ca2^ix	3.208 (2)
Ca1—Ca2	3.787 (5)	Bi1—Bi1^iii	3.4433 (14)
Ca1—Ca2^i	3.958 (4)	Bi1—Ca1^ix	3.623 (3)
Ca1—Ca2^v	3.958 (4)	Bi1—Ca1^i	3.7523 (9)
Ca1—Ca4	4.004 (6)	Bi1—Ca1^iii	3.7523 (11)
Ca1—Ca3^iii	4.037 (3)	Bi2—Ca3^xvii	3.0234 (7)
Ca2—Bi1^ii	3.208 (2)	Bi2—Ca2^vii	3.271 (3)
Ca2—Bi1	3.208 (2)	Bi2—Ca2^viii	3.271 (3)
Ca2—Bi5	3.247 (3)	Bi2—Ca2^vi	3.271 (3)
Ca2—Bi2	3.271 (3)	Bi2—Ca1^i	3.509 (4)
Ca2—Bi2^vi	3.271 (3)	Bi2—Ca1^xi	3.509 (4)
Ca2—Ca2^vii	3.562 (7)	In3—Bi3^ii	3.019 (2)
Ca2—In3	3.563 (3)	In3—Bi3^xvi	3.019 (2)
Ca2—Bi3^ii	3.563 (3)	In3—In3^ii	3.019 (2)
Ca2—In3^ii	3.563 (3)	In3—In3^xvi	3.019 (2)
Ca2—Ca2^viii	3.951 (7)	In3—Bi1^vii	3.1768 (11)
Ca3—Bi2^ix	3.0234 (7)	In3—Ca2^ix	3.563 (3)
Ca3—Bi2	3.0234 (7)	In3—Ca2^xviii	3.563 (3)
Ca3—Bi1^vii	3.660 (5)	In3—Ca2^vii	3.563 (3)
Ca3—Bi1	3.660 (5)	In3—Ca4^xv	3.585 (6)
Ca3—In3	3.689 (7)	Bi4—Ca1^xix	3.268 (4)
Ca3—Bi4^iii	3.709 (6)	Bi4—Ca1^xiii	3.268 (4)
Ca3—Bi4^x	3.709 (6)	Bi4—Ca1^ix	3.268 (4)
Ca3—Ca1^i	4.036 (3)	Bi4—Ca3^iii	3.709 (6)
Ca3—Ca1^iii	4.036 (3)	Bi4—Ca3^xx	3.709 (6)
Ca3—Ca1^xi	4.036 (3)	Bi4—Ca3^iv	3.709 (6)
Ca3—Ca1^xii	4.036 (3)	Bi4—Ca3^xxi	3.709 (6)
Ca4—Bi1	3.5308 (7)	Bi5—Ca1^v	3.244 (4)
Ca4—Bi1^xiii	3.5309 (7)	Bi5—Ca1^viii	3.244 (4)
Ca4—Bi1^xiv	3.5309 (7)	Bi5—Ca1^i	3.244 (4)
Ca4—Bi1^ii	3.5309 (7)	Bi5—Ca2^i	3.247 (3)
Ca4—Bi4	3.539 (7)	Bi5—Ca2^v	3.247 (3)
Ca4—Bi3^xv	3.585 (6)	Bi5—Ca2^viii	3.247 (3)
Bi5—Ca1—Bi4	179.21 (13)	Bi3^xv—Ca4—In3^ii	49.8
Bi5—Ca1—Bi2^i	89.45 (9)	In3^xv—Ca4—In3^ii	49.79 (9)
Bi4—Ca1—Bi2^i	91.34 (9)	Bi3^ii—Ca4—In3^ii	0.0
Bi5—Ca1—Bi1	86.08 (7)	Bi3^xvi—Ca4—In3^ii	73.1
Bi4—Ca1—Bi1	93.35 (8)	Bi1—Ca4—In3^xvi	89.65 (9)
Bi2^i—Ca1—Bi1	136.11 (4)	Bi1^xiii—Ca4—In3^xvi	89.65 (9)
Bi5—Ca1—Bi1^ii	86.08 (7)	Bi1^xiv—Ca4—In3^xvi	53.02 (5)
Bi4—Ca1—Bi1^ii	93.35 (8)	Bi1^ii—Ca4—In3^xvi	126.10 (18)
Bi2^i—Ca1—Bi1^ii	136.11 (4)	Bi4—Ca4—In3^xvi	143.46 (7)
Bi1—Ca1—Bi1^ii	87.13 (8)	Bi3^xv—Ca4—In3^xvi	49.8
Bi5—Ca1—Bi1^iii	83.96 (5)	In3^xv—Ca4—In3^xvi	49.79 (9)
Bi4—Ca1—Bi1^iii	96.17 (6)	Bi3^ii—Ca4—In3^xvi	73.1
Bi2^i—Ca1—Bi1^iii	80.47 (6)	Bi3^xvi—Ca4—In3^xvi	0.0
Bi1—Ca1—Bi1^iii	55.63 (3)	In3^ii—Ca4—In3^xvi	73.07 (14)
Bi1^ii—Ca1—Bi1^iii	141.94 (10)	In3—Bi1—Ca2	67.85 (6)
Bi5—Ca1—Bi1^iv	83.96 (5)	In3—Bi1—Ca2^ix	67.85 (6)
Bi4—Ca1—Bi1^iv	96.17 (6)	Ca2—Bi1—Ca2^ix	135.68 (13)
Bi2^i—Ca1—Bi1^iv	80.48 (6)	In3—Bi1—Bi1^iii	176.99 (4)
Bi1—Ca1—Bi1^iv	141.94 (10)	Ca2—Bi1—Bi1^iii	112.15 (6)
Bi1^ii—Ca1—Bi1^iv	55.63 (3)	Ca2^ix—Bi1—Bi1^iii	112.15 (6)
Bi1^iii—Ca1—Bi1^iv	157.48 (11)	In3—Bi1—Ca4	64.37 (12)
Bi5—Ca1—Ca2	54.35 (8)	Ca2—Bi1—Ca4	80.10 (7)
Bi4—Ca1—Ca2	124.86 (12)	Ca2^ix—Bi1—Ca4	80.10 (7)
Bi2^i—Ca1—Ca2	143.79 (12)	Bi1^iii—Bi1—Ca4	118.64 (12)
Bi1—Ca1—Ca2	51.25 (5)	In3—Bi1—Ca1	118.11 (5)
Bi1^ii—Ca1—Ca2	51.25 (5)	Ca2—Bi1—Ca1	67.03 (8)
Bi1^iii—Ca1—Ca2	94.15 (6)	Ca2^ix—Bi1—Ca1	137.14 (8)
Bi1^iv—Ca1—Ca2	94.15 (6)	Bi1^iii—Bi1—Ca1	64.09 (5)
Bi5—Ca1—Ca2^i	52.47 (6)	Ca4—Bi1—Ca1	68.06 (10)
Bi4—Ca1—Ca2^i	128.14 (10)	In3—Bi1—Ca1^ix	118.11 (5)
Bi2^i—Ca1—Ca2^i	51.53 (7)	Ca2—Bi1—Ca1^ix	137.14 (8)
Bi1—Ca1—Ca2^i	93.38 (7)	Ca2^ix—Bi1—Ca1^ix	67.03 (8)
Bi1^ii—Ca1—Ca2^i	138.32 (11)	Bi1^iii—Bi1—Ca1^ix	64.09 (4)
Bi1^iii—Ca1—Ca2^i	49.08 (5)	Ca4—Bi1—Ca1^ix	68.06 (10)
Bi1^iv—Ca1—Ca2^i	108.91 (9)	Ca1—Bi1—Ca1^ix	74.67 (11)
Ca2—Ca1—Ca2^i	98.38 (10)	In3—Bi1—Ca3	64.85 (9)
Bi5—Ca1—Ca2^v	52.47 (6)	Ca2—Bi1—Ca3	81.29 (6)
Bi4—Ca1—Ca2^v	128.14 (10)	Ca2^ix—Bi1—Ca3	81.29 (6)
Bi2^i—Ca1—Ca2^v	51.53 (7)	Bi1^iii—Bi1—Ca3	112.14 (9)
Bi1—Ca1—Ca2^v	138.32 (11)	Ca4—Bi1—Ca3	129.22 (15)
Bi1^ii—Ca1—Ca2^v	93.38 (7)	Ca1—Bi1—Ca3	141.26 (6)
Bi1^iii—Ca1—Ca2^v	108.91 (9)	Ca1^ix—Bi1—Ca3	141.26 (6)
Bi1^iv—Ca1—Ca2^v	49.08 (5)	In3—Bi1—Ca1^i	117.48 (6)
Ca2—Ca1—Ca2^v	98.38 (10)	Ca2—Bi1—Ca1^i	68.80 (8)
Ca2^i—Ca1—Ca2^v	59.88 (10)	Ca2^ix—Bi1—Ca1^i	136.28 (7)
Bi5—Ca1—Ca4	122.04 (13)	Bi1^iii—Bi1—Ca1^i	60.27 (6)
Bi4—Ca1—Ca4	57.17 (10)	Ca4—Bi1—Ca1^i	143.18 (6)
Bi2^i—Ca1—Ca4	148.52 (13)	Ca1—Bi1—Ca1^i	81.63 (10)
Bi1—Ca1—Ca4	54.88 (7)	Ca1^ix—Bi1—Ca1^i	124.37 (3)
Bi1^ii—Ca1—Ca4	54.88 (7)	Ca3—Bi1—Ca1^i	65.97 (9)
Bi1^iii—Ca1—Ca4	101.26 (6)	In3—Bi1—Ca1^iii	117.48 (6)
Bi1^iv—Ca1—Ca4	101.26 (6)	Ca2—Bi1—Ca1^iii	136.29 (7)
Ca2—Ca1—Ca4	67.69 (11)	Ca2^ix—Bi1—Ca1^iii	68.80 (8)
Ca2^i—Ca1—Ca4	147.73 (7)	Bi1^iii—Bi1—Ca1^iii	60.27 (6)
Ca2^v—Ca1—Ca4	147.73 (7)	Ca4—Bi1—Ca1^iii	143.18 (6)
Bi5—Ca1—Ca3^iii	120.70 (12)	Ca1—Bi1—Ca1^iii	124.37 (3)
Bi4—Ca1—Ca3^iii	59.93 (11)	Ca1^ix—Bi1—Ca1^iii	81.62 (10)
Bi2^i—Ca1—Ca3^iii	46.59 (5)	Ca3—Bi1—Ca1^iii	65.97 (9)
Bi1—Ca1—Ca3^iii	100.52 (5)	Ca1^i—Bi1—Ca1^iii	71.67 (11)
Bi1^ii—Ca1—Ca3^iii	152.34 (14)	Ca3^xvii—Bi2—Ca3	85.9 (3)
Bi1^iii—Ca1—Ca3^iii	55.92 (9)	Ca3^xvii—Bi2—Ca2^vii	146.88 (6)
Bi1^iv—Ca1—Ca3^iii	116.12 (11)	Ca3—Bi2—Ca2^vii	90.85 (12)
Ca2—Ca1—Ca3^iii	149.32 (8)	Ca3^xvii—Bi2—Ca2^viii	90.85 (12)
Ca2^i—Ca1—Ca3^iii	68.28 (11)	Ca3—Bi2—Ca2^viii	146.88 (6)
Ca2^v—Ca1—Ca3^iii	98.00 (10)	Ca2^vii—Bi2—Ca2^viii	108.81 (8)
Ca4—Ca1—Ca3^iii	108.41 (11)	Ca3^xvii—Bi2—Ca2^vi	90.85 (12)
Bi1^ii—Ca2—Bi1	102.21 (10)	Ca3—Bi2—Ca2^vi	146.88 (6)
Bi1^ii—Ca2—Bi5	93.32 (8)	Ca2^vii—Bi2—Ca2^vi	74.31 (11)
Bi1—Ca2—Bi5	93.32 (8)	Ca2^viii—Bi2—Ca2^vi	65.98 (11)
Bi1^ii—Ca2—Bi2	162.95 (9)	Ca3^xvii—Bi2—Ca2	146.88 (6)
Bi1—Ca2—Bi2	92.87 (2)	Ca3—Bi2—Ca2	90.85 (12)
Bi5—Ca2—Bi2	93.71 (8)	Ca2^vii—Bi2—Ca2	65.98 (11)
Bi1^ii—Ca2—Bi2^vi	92.87 (3)	Ca2^viii—Bi2—Ca2	74.31 (11)
Bi1—Ca2—Bi2^vi	162.95 (9)	Ca2^vi—Bi2—Ca2	108.81 (8)
Bi5—Ca2—Bi2^vi	93.71 (8)	Ca3^xvii—Bi2—Ca1^i	75.92 (5)
Bi2—Ca2—Bi2^vi	71.19 (8)	Ca3—Bi2—Ca1^i	75.92 (5)
Bi1^ii—Ca2—Ca2^vii	109.54 (6)	Ca2^vii—Bi2—Ca1^i	134.99 (7)
Bi1—Ca2—Ca2^vii	109.54 (6)	Ca2^viii—Bi2—Ca1^i	71.33 (7)
Bi5—Ca2—Ca2^vii	142.53 (6)	Ca2^vi—Bi2—Ca1^i	134.99 (7)
Bi2—Ca2—Ca2^vii	57.01 (6)	Ca2—Bi2—Ca1^i	71.33 (7)
Bi2^vi—Ca2—Ca2^vii	57.01 (6)	Ca3^xvii—Bi2—Ca1^xi	75.92 (5)
Bi1^ii—Ca2—In3	95.47 (9)	Ca3—Bi2—Ca1^xi	75.92 (5)
Bi1—Ca2—In3	55.66 (4)	Ca2^vii—Bi2—Ca1^xi	71.33 (7)
Bi5—Ca2—In3	148.90 (7)	Ca2^viii—Bi2—Ca1^xi	134.99 (7)
Bi2—Ca2—In3	86.42 (6)	Ca2^vi—Bi2—Ca1^xi	71.33 (7)
Bi2^vi—Ca2—In3	115.51 (10)	Ca2—Bi2—Ca1^xi	134.99 (7)
Ca2^vii—Ca2—In3	60.02 (6)	Ca1^i—Bi2—Ca1^xi	141.19 (12)
Bi1^ii—Ca2—Bi3^ii	55.66 (4)	Bi3^ii—In3—Bi3^xvi	90.0
Bi1—Ca2—Bi3^ii	95.47 (9)	Bi3^ii—In3—In3^ii	0.0
Bi5—Ca2—Bi3^ii	148.90 (7)	Bi3^xvi—In3—In3^ii	90.0
Bi2—Ca2—Bi3^ii	115.51 (10)	Bi3^ii—In3—In3^xvi	90.0
Bi2^vi—Ca2—Bi3^ii	86.42 (6)	Bi3^xvi—In3—In3^xvi	0.0
Ca2^vii—Ca2—Bi3^ii	60.02 (6)	In3^ii—In3—In3^xvi	90.0
In3—Ca2—Bi3^ii	50.1	Bi3^ii—In3—Bi1^vii	108.11 (2)
Bi1^ii—Ca2—In3^ii	55.66 (4)	Bi3^xvi—In3—Bi1^vii	108.11 (2)
Bi1—Ca2—In3^ii	95.47 (9)	In3^ii—In3—Bi1^vii	108.11 (2)
Bi5—Ca2—In3^ii	148.90 (7)	In3^xvi—In3—Bi1^vii	108.11 (2)
Bi2—Ca2—In3^ii	115.51 (10)	Bi3^ii—In3—Bi1	108.11 (2)
Bi2^vi—Ca2—In3^ii	86.42 (6)	Bi3^xvi—In3—Bi1	108.11 (2)
Ca2^vii—Ca2—In3^ii	60.02 (6)	In3^ii—In3—Bi1	108.11 (2)
In3—Ca2—In3^ii	50.12 (7)	In3^xvi—In3—Bi1	108.11 (2)
Bi3^ii—Ca2—In3^ii	0.0	Bi1^vii—In3—Bi1	127.85 (6)
Bi1^ii—Ca2—Ca1	61.72 (6)	Bi3^ii—In3—Ca2	64.94 (3)
Bi1—Ca2—Ca1	61.72 (6)	Bi3^xvi—In3—Ca2	139.07 (5)
Bi5—Ca2—Ca1	54.26 (8)	In3^ii—In3—Ca2	64.94 (3)
Bi2—Ca2—Ca1	134.09 (8)	In3^xvi—In3—Ca2	139.07 (5)
Bi2^vi—Ca2—Ca1	134.09 (8)	Bi1^vii—In3—Ca2	110.23 (6)
Ca2^vii—Ca2—Ca1	163.20 (7)	Bi1—In3—Ca2	56.49 (4)
In3—Ca2—Ca1	105.08 (9)	Bi3^ii—In3—Ca2^ix	139.07 (5)
Bi3^ii—Ca2—Ca1	105.08 (9)	Bi3^xvi—In3—Ca2^ix	64.94 (3)
In3^ii—Ca2—Ca1	105.08 (9)	In3^ii—In3—Ca2^ix	139.07 (5)
Bi1^ii—Ca2—Ca2^viii	122.10 (5)	In3^xvi—In3—Ca2^ix	64.94 (3)
Bi1—Ca2—Ca2^viii	122.10 (5)	Bi1^vii—In3—Ca2^ix	110.23 (6)
Bi5—Ca2—Ca2^viii	52.53 (6)	Bi1—In3—Ca2^ix	56.49 (4)
Bi2—Ca2—Ca2^viii	52.85 (5)	Ca2—In3—Ca2^ix	112.97 (9)
Bi2^vi—Ca2—Ca2^viii	52.85 (5)	Bi3^ii—In3—Ca2^xviii	139.07 (5)
Ca2^vii—Ca2—Ca2^viii	90.0	Bi3^xvi—In3—Ca2^xviii	64.94 (3)
In3—Ca2—Ca2^viii	139.07 (5)	In3^ii—In3—Ca2^xviii	139.07 (5)
Bi3^ii—Ca2—Ca2^viii	139.07 (5)	In3^xvi—In3—Ca2^xviii	64.94 (3)
In3^ii—Ca2—Ca2^viii	139.07 (5)	Bi1^vii—In3—Ca2^xviii	56.49 (4)
Ca1—Ca2—Ca2^viii	106.80 (7)	Bi1—In3—Ca2^xviii	110.23 (6)
Bi2^ix—Ca3—Bi2	175.9 (3)	Ca2—In3—Ca2^xviii	152.85 (8)
Bi2^ix—Ca3—Bi1^vii	88.70 (9)	Ca2^ix—In3—Ca2^xviii	59.97 (11)
Bi2—Ca3—Bi1^vii	88.70 (9)	Bi3^ii—In3—Ca2^vii	64.94 (3)
Bi2^ix—Ca3—Bi1	88.70 (9)	Bi3^xvi—In3—Ca2^vii	139.07 (5)
Bi2—Ca3—Bi1	88.70 (9)	In3^ii—In3—Ca2^vii	64.94 (3)
Bi1^vii—Ca3—Bi1	102.45 (18)	In3^xvi—In3—Ca2^vii	139.07 (5)
Bi2^ix—Ca3—In3	87.93 (14)	Bi1^vii—In3—Ca2^vii	56.49 (4)
Bi2—Ca3—In3	87.93 (14)	Bi1—In3—Ca2^vii	110.23 (6)
Bi1^vii—Ca3—In3	51.22 (9)	Ca2—In3—Ca2^vii	59.97 (11)
Bi1—Ca3—In3	51.22 (9)	Ca2^ix—In3—Ca2^vii	152.85 (8)
Bi2^ix—Ca3—Bi4^iii	91.63 (11)	Ca2^xviii—In3—Ca2^vii	112.97 (9)
Bi2—Ca3—Bi4^iii	91.63 (11)	Bi3^ii—In3—Ca4	65.10 (4)
Bi1^vii—Ca3—Bi4^iii	167.03 (16)	Bi3^xvi—In3—Ca4	65.10 (4)
Bi1—Ca3—Bi4^iii	90.52 (3)	In3^ii—In3—Ca4	65.10 (4)
In3—Ca3—Bi4^iii	141.74 (7)	In3^xvi—In3—Ca4	65.10 (4)
Bi2^ix—Ca3—Bi4^x	91.63 (11)	Bi1^vii—In3—Ca4	169.54 (8)
Bi2—Ca3—Bi4^x	91.63 (11)	Bi1—In3—Ca4	62.61 (7)
Bi1^vii—Ca3—Bi4^x	90.52 (3)	Ca2—In3—Ca4	74.82 (6)
Bi1—Ca3—Bi4^x	167.03 (16)	Ca2^ix—In3—Ca4	74.82 (6)
In3—Ca3—Bi4^x	141.74 (7)	Ca2^xviii—In3—Ca4	122.77 (4)
Bi4^iii—Ca3—Bi4^x	76.52 (14)	Ca2^vii—In3—Ca4	122.77 (4)
Bi2^ix—Ca3—Ca1^i	123.39 (5)	Bi3^ii—In3—Ca4^xv	65.10 (4)
Bi2—Ca3—Ca1^i	57.49 (5)	Bi3^xvi—In3—Ca4^xv	65.10 (4)
Bi1^vii—Ca3—Ca1^i	138.61 (14)	In3^ii—In3—Ca4^xv	65.10 (4)
Bi1—Ca3—Ca1^i	58.11 (4)	In3^xvi—In3—Ca4^xv	65.10 (4)
In3—Ca3—Ca1^i	100.21 (11)	Bi1^vii—In3—Ca4^xv	62.61 (7)
Bi4^iii—Ca3—Ca1^i	49.69 (7)	Bi1—In3—Ca4^xv	169.54 (8)
Bi4^x—Ca3—Ca1^i	111.63 (15)	Ca2—In3—Ca4^xv	122.77 (4)
Bi2^ix—Ca3—Ca1^iii	57.49 (5)	Ca2^ix—In3—Ca4^xv	122.77 (4)
Bi2—Ca3—Ca1^iii	123.39 (5)	Ca2^xviii—In3—Ca4^xv	74.82 (6)
Bi1^vii—Ca3—Ca1^iii	138.61 (14)	Ca2^vii—In3—Ca4^xv	74.82 (6)
Bi1—Ca3—Ca1^iii	58.11 (4)	Ca4—In3—Ca4^xv	106.93 (14)
In3—Ca3—Ca1^iii	100.21 (11)	Ca1—Bi4—Ca1^xix	84.48 (4)
Bi4^iii—Ca3—Ca1^iii	49.69 (7)	Ca1—Bi4—Ca1^xiii	143.87 (14)
Bi4^x—Ca3—Ca1^iii	111.63 (15)	Ca1^xix—Bi4—Ca1^xiii	84.48 (4)
Ca1^i—Ca3—Ca1^iii	65.95 (9)	Ca1—Bi4—Ca1^ix	84.48 (4)
Bi2^ix—Ca3—Ca1^xi	123.39 (5)	Ca1^xix—Bi4—Ca1^ix	143.87 (14)
Bi2—Ca3—Ca1^xi	57.49 (5)	Ca1^xiii—Bi4—Ca1^ix	84.48 (4)
Bi1^vii—Ca3—Ca1^xi	58.11 (4)	Ca1—Bi4—Ca4	71.93 (7)
Bi1—Ca3—Ca1^xi	138.61 (14)	Ca1^xix—Bi4—Ca4	71.94 (7)
In3—Ca3—Ca1^xi	100.21 (11)	Ca1^xiii—Bi4—Ca4	71.94 (7)
Bi4^iii—Ca3—Ca1^xi	111.63 (15)	Ca1^ix—Bi4—Ca4	71.94 (7)
Bi4^x—Ca3—Ca1^xi	49.69 (7)	Ca1—Bi4—Ca3^iii	70.38 (7)
Ca1^i—Ca3—Ca1^xi	110.17 (9)	Ca1^xix—Bi4—Ca3^iii	136.04 (5)
Ca1^iii—Ca3—Ca1^xi	159.6 (2)	Ca1^xiii—Bi4—Ca3^iii	136.04 (5)
Bi2^ix—Ca3—Ca1^xii	57.49 (5)	Ca1^ix—Bi4—Ca3^iii	70.38 (7)
Bi2—Ca3—Ca1^xii	123.39 (5)	Ca4—Bi4—Ca3^iii	128.26 (7)
Bi1^vii—Ca3—Ca1^xii	58.11 (4)	Ca1—Bi4—Ca3^xx	136.04 (5)
Bi1—Ca3—Ca1^xii	138.61 (14)	Ca1^xix—Bi4—Ca3^xx	136.04 (5)
In3—Ca3—Ca1^xii	100.21 (11)	Ca1^xiii—Bi4—Ca3^xx	70.38 (7)
Bi4^iii—Ca3—Ca1^xii	111.63 (15)	Ca1^ix—Bi4—Ca3^xx	70.38 (7)
Bi4^x—Ca3—Ca1^xii	49.69 (7)	Ca4—Bi4—Ca3^xx	128.26 (7)
Ca1^i—Ca3—Ca1^xii	159.6 (2)	Ca3^iii—Bi4—Ca3^xx	67.45 (7)
Ca1^iii—Ca3—Ca1^xii	110.17 (9)	Ca1—Bi4—Ca3^iv	70.38 (7)
Ca1^xi—Ca3—Ca1^xii	65.95 (9)	Ca1^xix—Bi4—Ca3^iv	70.38 (7)
Bi1—Ca4—Bi1^xiii	179.1 (2)	Ca1^xiii—Bi4—Ca3^iv	136.04 (5)
Bi1—Ca4—Bi1^xiv	89.997 (9)	Ca1^ix—Bi4—Ca3^iv	136.04 (5)
Bi1^xiii—Ca4—Bi1^xiv	89.997 (9)	Ca4—Bi4—Ca3^iv	128.26 (7)
Bi1—Ca4—Bi1^ii	89.997 (9)	Ca3^iii—Bi4—Ca3^iv	67.45 (7)
Bi1^xiii—Ca4—Bi1^ii	89.997 (9)	Ca3^xx—Bi4—Ca3^iv	103.48 (14)
Bi1^xiv—Ca4—Bi1^ii	179.1 (2)	Ca1—Bi4—Ca3^xxi	136.04 (5)
Bi1—Ca4—Bi4	90.44 (12)	Ca1^xix—Bi4—Ca3^xxi	70.38 (7)
Bi1^xiii—Ca4—Bi4	90.44 (12)	Ca1^xiii—Bi4—Ca3^xxi	70.38 (7)
Bi1^xiv—Ca4—Bi4	90.44 (12)	Ca1^ix—Bi4—Ca3^xxi	136.04 (5)
Bi1^ii—Ca4—Bi4	90.44 (12)	Ca4—Bi4—Ca3^xxi	128.26 (7)
Bi1—Ca4—Bi3^xv	126.10 (18)	Ca3^iii—Bi4—Ca3^xxi	103.48 (14)
Bi1^xiii—Ca4—Bi3^xv	53.02 (5)	Ca3^xx—Bi4—Ca3^xxi	67.45 (7)
Bi1^xiv—Ca4—Bi3^xv	89.65 (9)	Ca3^iv—Bi4—Ca3^xxi	67.45 (7)
Bi1^ii—Ca4—Bi3^xv	89.65 (9)	Ca1^v—Bi5—Ca1^viii	95.99 (4)
Bi4—Ca4—Bi3^xv	143.46 (7)	Ca1^v—Bi5—Ca1^i	142.29 (13)
Bi1—Ca4—In3^xv	126.10 (18)	Ca1^viii—Bi5—Ca1^i	95.99 (4)
Bi1^xiii—Ca4—In3^xv	53.02 (5)	Ca1^v—Bi5—Ca1	95.99 (4)
Bi1^xiv—Ca4—In3^xv	89.65 (9)	Ca1^viii—Bi5—Ca1	142.29 (13)
Bi1^ii—Ca4—In3^xv	89.65 (9)	Ca1^i—Bi5—Ca1	95.99 (4)
Bi4—Ca4—In3^xv	143.46 (7)	Ca1^v—Bi5—Ca2	75.14 (5)
Bi3^xv—Ca4—In3^xv	0.0	Ca1^viii—Bi5—Ca2	146.32 (9)
Bi1—Ca4—Bi3^ii	89.65 (9)	Ca1^i—Bi5—Ca2	75.14 (5)
Bi1^xiii—Ca4—Bi3^ii	89.65 (9)	Ca1—Bi5—Ca2	71.39 (9)
Bi1^xiv—Ca4—Bi3^ii	126.10 (18)	Ca1^v—Bi5—Ca2^i	146.32 (9)
Bi1^ii—Ca4—Bi3^ii	53.02 (5)	Ca1^viii—Bi5—Ca2^i	75.14 (5)
Bi4—Ca4—Bi3^ii	143.46 (7)	Ca1^i—Bi5—Ca2^i	71.39 (9)
Bi3^xv—Ca4—Bi3^ii	49.79 (9)	Ca1—Bi5—Ca2^i	75.14 (5)
In3^xv—Ca4—Bi3^ii	49.79 (9)	Ca2—Bi5—Ca2^i	129.05 (8)
Bi1—Ca4—Bi3^xvi	89.65 (9)	Ca1^v—Bi5—Ca2^v	71.39 (9)
Bi1^xiii—Ca4—Bi3^xvi	89.65 (9)	Ca1^viii—Bi5—Ca2^v	75.14 (5)
Bi1^xiv—Ca4—Bi3^xvi	53.02 (5)	Ca1^i—Bi5—Ca2^v	146.32 (9)
Bi1^ii—Ca4—Bi3^xvi	126.10 (18)	Ca1—Bi5—Ca2^v	75.14 (5)
Bi4—Ca4—Bi3^xvi	143.46 (7)	Ca2—Bi5—Ca2^v	129.05 (8)
Bi3^xv—Ca4—Bi3^xvi	49.79 (9)	Ca2^i—Bi5—Ca2^v	74.93 (12)
In3^xv—Ca4—Bi3^xvi	49.79 (9)	Ca1^v—Bi5—Ca2^viii	75.14 (5)
Bi3^ii—Ca4—Bi3^xvi	73.07 (14)	Ca1^viii—Bi5—Ca2^viii	71.39 (9)
Bi1—Ca4—In3^ii	89.65 (9)	Ca1^i—Bi5—Ca2^viii	75.14 (5)
Bi1^xiii—Ca4—In3^ii	89.65 (9)	Ca1—Bi5—Ca2^viii	146.32 (9)
Bi1^xiv—Ca4—In3^ii	126.10 (18)	Ca2—Bi5—Ca2^viii	74.93 (12)
Bi1^ii—Ca4—In3^ii	53.02 (5)	Ca2^i—Bi5—Ca2^viii	129.05 (8)
Bi4—Ca4—In3^ii	143.46 (7)	Ca2^v—Bi5—Ca2^viii	129.05 (8)

Symmetry codes: (i) −y+1/2, −x+1/2, −z+1/2; (ii) −x, y, z; (iii) −x+1/2, −y+1/2, −z+1/2; (iv) x−1/2, −y+1/2, −z+1/2; (v) y−1/2, x+1/2, −z+1/2; (vi) −x, −y+1, −z; (vii) x, y, −z; (viii) −x, −y+1, z; (ix) y, x, z; (x) x+1/2, y+1/2, z−1/2; (xi) −y+1/2, −x+1/2, z−1/2; (xii) −x+1/2, −y+1/2, z−1/2; (xiii) −x, −y, z; (xiv) x, −y, z; (xv) −x, −y, −z; (xvi) x, −y, −z; (xvii) x, −y+1, −z; (xviii) y, x, −z; (xix) −y, −x, z; (xx) −x+1/2, y−1/2, z+1/2; (xxi) x−1/2, y−1/2, z+1/2.